Semiconductor device and method for manufacturing the same

ABSTRACT

It is possible to prevent the deterioration of device characteristic as much as possible. A semiconductor device includes: a semiconductor substrate; a gate insulating film provided above the semiconductor substrate and containing a metal, oxygen and an additive element; a gate electrode provided above the gate insulating film; and source/drain regions provided in the semiconductor substrate on both sides of the gate electrode. The additive element is at least one element selected from elements of Group 5, 6, 15, and 16 at a concentration of 0.003 atomic % or more but 3 atomic % or less.

CROSS-REFERENCE TO RELATED APPLICATION

This application is based upon and claims the benefit of priority fromprior Japanese Patent Application No. 2005-232979 filed on Aug. 11, 2005in Japan, the entire contents of which are incorporated herein byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a semiconductor device and a method formanufacturing the same.

2. Related Art

In MOS transistors, an increase in leakage current between a gate and asubstrate resulting from direct tunneling of carriers through aninsulating film is an issue. As a method for avoiding such tunneling,formation of a gate insulating film using a material having a relativedielectric constant significantly higher than that of SiO₂ has beenproposed. Specific examples of such a gate insulating film include metaloxide films made of high-dielectric constant metal oxides such as ZrO₂and HfO₂ and metal oxide films made of compounds of such high-dielectricconstant metal oxides and SiO₂, i.e., so-called silicates. Further,silicates containing nitrogen can maintain an amorphous state even at1,000° C., and have a high relative dielectric constant of about 20. Inaddition, the diffusion coefficient of an impurity such as boron in suchN-containing silicate films is small. For these reasons, N-containingsilicate films are expected to be applied to a CMOS process requiringheat resistance.

However, in a case where a gate electrode made of polycrystallinesilicon and a gate insulating film made of a metal oxide such as HfO₂ orZrO₂ are used together, a threshold voltage fluctuates. The degree offluctuation is very large, and therefore it is difficult to control athreshold voltage by a conventional method, that is, by adjusting theimpurity concentration of a substrate portion. Further, it has beenconfirmed that such a phenomenon can occur not only when puresemiconductor gate electrodes of, for example, Si or Ge are used, butalso when semiconductor gate electrodes of metal silicides or metalgermanides are used.

In order to solve such a problem, a method for suppressing fluctuationsin threshold voltage has been proposed (see, for example, JapanesePatent Laid-open Publication No. 2002-280461). According to this method,an additive element having a valence higher than that of a metalconstituting a high-dielectric constant film by one is added to an N-MIStransistor and an additive element having a valence lower than that of ametal constituting a high-dielectric constant film by one is added to aP-MIS transistor so that charge states thereof are different from eachother, thereby suppressing fluctuations in threshold voltage.

However, addition of different additive elements to the N-MIS transistorand the P-MIS transistor complicates a manufacturing process, therebyincreasing manufacturing costs as a whole.

Further, in order to achieve a low threshold voltage, it is necessary toadd a high concentration (10 atomic %) of additive element. When theconcentration of the additive element is high, it is impossible toneglect the characteristics of the additive element itself. For example,excessive addition of the additive element leads to a decrease indielectric constant. Further, excessive addition of the additive elementallows a large number of fixed charges to exist in the insulating filmso that electrons or holes as transistor carriers are scattered by thefixed charges existing in the insulating film, thus resulting indecrease in electron mobility or hole mobility. As described above,introduction of a high concentration of additive element into a gateinsulating film made of a metal oxide leads to a decrease in dielectricconstant and a decrease in electron mobility or hole mobility, therebycausing a problem that device characteristics are deteriorated.

SUMMARY OF THE INVENTION

Under the circumstances, it is an object of the present invention toprovide a semiconductor device capable of preventing deterioration ofdevice characteristics as much as possible and a method formanufacturing such a semiconductor device.

A semiconductor device according to a first aspect of the presentinvention includes: a semiconductor substrate; a gate insulating filmprovided above the semiconductor substrate and containing a metal,oxygen and an additive element; a gate electrode provided above the gateinsulating film; and source/drain regions provided in the semiconductorsubstrate on both sides of the gate electrode, the additive elementbeing at least one element selected from elements of Group 5, 6, 15, and16 at a concentration of 0.003 atomic % or more but 3 atomic % or less.

A semiconductor device according to a second aspect of the presentinvention includes: a semiconductor substrate; a gate insulating filmprovided above the semiconductor substrate; a first gate electrodeprovided above the gate insulating film; an interelectrode insulatingfilm provided above the first gate electrode and containing a metal,oxygen and an additive element; a second gate electrode provided abovethe interelectrode insulating film; and source/drain regions provided inthe semiconductor substrate on both sides of the first and second gateelectrodes, the additive element being at least one element selectedfrom elements of Group 5, 6, 15, and 16 at a concentration of 0.003atomic % or more but 3 atomic % or less.

A method for manufacturing a semiconductor device according to a thirdaspect of the present invention includes: forming a gate insulating filmwhich contains a metal, oxygen, and 0.003 atomic % or more but 3 atomic% or less of at least one additive element selected from elements ofGroup 5, 6, 15, and 16, above a semiconductor substrate; forming a gateelectrode above the gate insulating film; and forming source/drainregions by introducing an impurity into an element region of thesemiconductor substrate by using the gate electrode as a mask.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view which shows the bonding state of a metal,oxygen, and an additive element in a metal oxide film constituting agate insulating film of a semiconductor device according to a firstembodiment of the present invention;

FIG. 2 shows an XPS spectrum representing the bonding state of Sb addedto the gate insulating film of the semiconductor device according to thefirst embodiment of the present invention and an XPS spectrumrepresenting the bonding state of Sb added to a gate insulating film ofa semiconductor device according to a comparative example;

FIG. 3 is a graph which shows the gate leakage current characteristicsof the semiconductor device according to the first embodiment of thepresent invention and the gate leakage current characteristics ofsemiconductor devices according to comparative examples 1 and 2;

FIG. 4 is a graph which shows the capacitance-voltage characteristics ofsemiconductor devices according to the first embodiment of the presentinvention;

FIG. 5 is a graph which shows the capacitance-voltage characteristics ofconventional semiconductor devices;

FIG. 6 is a graph which shows the capacitance-voltage characteristics ofsemiconductor devices according to a comparative example;

FIG. 7 is a cross-sectional view of a semiconductor device according toa second embodiment of the present invention;

FIGS. 8A to 8C are cross-sectional views which show the manufacturingsteps of the semiconductor device according to the second embodiment ofthe present invention;

FIGS. 9A to 9C are cross-sectional views which show the manufacturingsteps of the semiconductor device according to the second embodiment ofthe present invention;

FIGS. 10A to 10C are cross-sectional views which show the manufacturingsteps of the semiconductor device according to the second embodiment ofthe present invention;

FIG. 11 is a cross-sectional view of a semiconductor device according toa third embodiment of the present invention;

FIG. 12 is a cross-sectional view which shows the manufacturing step ofthe semiconductor device according to the third embodiment of thepresent invention;

FIG. 13 is a cross-sectional view of a semiconductor device according toa fourth embodiment of the present invention;

FIGS. 14A to 14C are cross-sectional views which show the manufacturingsteps of the semiconductor device according to the fourth embodiment ofthe present invention;

FIGS. 15A to 15C are cross-sectional views which show the manufacturingsteps of the semiconductor device according to the fourth embodiment ofthe present invention;

FIGS. 16A to 16C are cross-sectional views which show the manufacturingsteps of the semiconductor device according to the fourth embodiment ofthe present invention;

FIG. 17 is a cross-sectional view which shows the manufacturing step ofthe semiconductor device according to a modification of the fourthembodiment of the present invention;

FIG. 18 is a cross-sectional view of a semiconductor device according toa modification of any one of the first to fourth embodiments of thepresent invention;

FIG. 19 is a cross-sectional view of a semiconductor device according toa modification of any one of the first to fourth embodiments of thepresent invention;

FIG. 20 is a cross-sectional view of a semiconductor device according toa modification of a fifth embodiment of the present invention;

FIGS. 21A to 21C are cross-sectional views which show the manufacturingsteps of the semiconductor device according to the fifth embodiment ofthe present invention;

FIGS. 22A to 22C are cross-sectional views which show the manufacturingsteps of the semiconductor device according to the fifth embodiment ofthe present invention;

FIGS. 23A to 23B are cross-sectional views which show the manufacturingsteps of the semiconductor device according to the fifth embodiment ofthe present invention; and

FIGS. 24A to 24B are cross-sectional views which show the manufacturingsteps of the semiconductor device according to the fifth embodiment ofthe present invention.

DETAILED DESCRIPTION OF THE INVENTION

Hereinbelow, embodiments of the present invention will be described withreference to the accompanying drawings.

FIRST EMBODIMENT

A semiconductor device according to a first embodiment of the presentinvention includes a MIS transistor comprising a gate insulating filmmade of a high-dielectric constant dielectric and provided on asemiconductor substrate, a gate electrode provided on the gateinsulating film, and source/drain regions provided in the semiconductorsubstrate on both sides of the gate electrode. The gate insulating filmcontains not only a metal and oxygen but also at least one elementselected from elements of Group 5, 6, 15, and 16 at a concentration of 3atomic % or less as an additive element. Hereinbelow, a gate insulatingfilm containing hafnium (Hf) as a metal and antimony (Sb) as an additiveelement will be described by way of example.

As schematically shown in FIG. 1, the metal and oxygen constituting thegate insulating film of the semiconductor device according to the firstembodiment are bonded together to form a metal oxide in the gateinsulating film. Further, as shown in FIG. 1, Hf and oxygen arepartially replaced with Sb added as the additive element so that Sb iscontained in the gate insulating film.

In the metal oxide used as a high-dielectric constant dielectric, alarge amount of oxygen vacancies are formed not only just after theformation of the gate insulating film but also in the step of formingthe gate electrode made of a semiconductor or the step of heat treatmentfor activation. The amount of oxygen vacancies to be formed variesdepending on conditions for forming the gate insulating film, conditionsfor forming the gate electrode made of a semiconductor, or heattreatment conditions for activation, but can reach 0.1 atomic %.However, the addition of Sb as the additive element makes it possible tosuppress the removal of oxygen from the gate insulating film. As shownin FIG. 1, both of Hf and oxygen can be replaced with Sb added as theadditive element. In either case, Sb added to the gate insulating filmis tightly bonded to oxygen contained in the gate insulating film tostabilize oxygen, thereby suppressing the removal of oxygen from thegate insulating film.

FIG. 2 shows an XPS (X-ray Photoelectron Spectroscopy) spectrumrepresenting the bonding state of Sb added to the gate insulating filmof the semiconductor device according to the first embodiment and an XPSspectrum representing the bonding state of Sb added to a gate insultingfilm of a semiconductor device according to a comparative example. Theconcentration of Sb added to the gate insulating film of thesemiconductor device according to the first embodiment is about 1.0atomic %, and the concentration of Sb added to the gate insulating filmof the semiconductor device according to the comparative example isabout 3.1 atomic %. As can be seen from FIG. 2, in both of thesemiconductor devices according to the first embodiment and thecomparative example, Sb is mainly bonded to oxygen, that is, Hf ismainly replaced with Sb so that Sb is contained in the gate insulatingfilm. In FIG. 2, an Hf—Sb bond is not detected, because the amount ofoxygen vacancies is 0.1 atomic % at most and therefore the amount ofHf-Sb bonds is less than an amount detectable by XPS. The bonding stateof such a trace amount of element can be evaluated by EELS (ElectronEnergy Loss Spectroscopy). EELS is an analytical method excellent inanalysis of elements having a relatively low atomic number. Therefore,EELS is preferably used for evaluation of phosphorus, arsenic, antimony,bismuth and the like.

In a case where Sb is excessively added, there is a fear that a decreasein dielectric constant causes an increase in leakage current. Since thedielectric constant of HfO₂ is about 20 and the dielectric constant ofSb₂O₃ is about 8, there is a possibility that excessive addition of Sbcauses an increase in leakage current due to a decrease in dielectricconstant.

FIG. 3 shows the difference in gate leakage current among semiconductordevices according to the first embodiment and comparative examples 1 and2 containing Sb at different concentrations. In the case of thesemiconductor device according to the first embodiment containing Sb at1.0 atomic %, gate leakage current is significantly decreased ascompared to the case of the semiconductor device according to thecomparative example 1 not containing Sb. This is because, in this case,addition of Sb has the effect of compensating for oxygen vacancy sitesin the high-dielectric constant insulating film rather than decreasingthe dielectric constant of the insulating film so that electron and holetrapping sites are decreased. On the other hand, in the case of thesemiconductor device according to the comparative example 2 containingSb at 3.1 atomic %, gate leakage current is slightly increased ascompared to the case of the semiconductor device according to the firstembodiment containing Sb at 1.0 atomic %. As a reason for this, it canbe considered that, as described above, excessive addition of Sbdecreases dielectric constant, thereby increasing leakage current.

FIG. 4 shows the capacitance-voltage characteristics of N-and P-typesilicon gate-MOS capacitors containing Sb at the same concentration asthe semiconductor device according to the first embodiment, that is, at1.0 atomic %. As shown in FIG. 4, the difference in flat-band voltagebetween the N- and P-type silicon gate-MOS capacitors containing Sb atthe same concentration as the semiconductor device according to thefirst embodiment, that is, at 1.0 atomic % is about 0.7 V. Therefore, itis possible to adjust a threshold voltage by ion implantation into achannel region, thereby suppressing fluctuations in flat-band voltage toan acceptable level for a MISFET for practical use. As a result, it ispossible to obtain a semiconductor device including a MIS transistorwhich can normally operate.

On the other hand, in the case of a conventional example containing noSb (Sb=0%) as shown in FIG. 5, the difference in flat-band voltagebetween N-type and P-type silicon gate-MOS capacitors is only about 0.3V. In this case, it is difficult to adjust a threshold voltage by ionimplantation into a channel region. Therefore, such semiconductordevices cannot be used as MISFETs.

In the case of a comparative example containing Sb at 3.1 atomic % asshown in FIG. 6, the difference in flat band voltage between N- andP-type silicon gate-MOS capacitors is enough, that is, 0.6 V. However,in this case, the capacitance of each of the MOS capacitors is decreaseddue to a decrease in dielectric constant, and the flat-band voltage ofeach of the MOS capacitors negatively shifts due to an increase in fixedcharge generated by Sb itself.

According to the above description and the findings of the presentinventors, the amount of the additive element is preferably 0.003 atomic% or more but 3 atomic % or less. By decreasing the amount of theadditive element to 3 atomic % or less, it is possible to suppress adecrease in electron mobility or hole mobility due to scattering ofelectrons or holes, caused by an increase in fixed charge, to anegligible level.

As has been described above, according to the first embodiment, it ispossible to prevent the deterioration of device characteristics as muchas possible and to avoid fluctuations in threshold voltage.

Further, according to the first embodiment, it is also possible to addthe same additive element to the N- and P-MIS transistors, and thereforea manufacturing process is simplified, thereby suppressing an increasein manufacturing costs.

SECOND EMBODIMENT

Hereinbelow, a semiconductor device according to a second embodiment ofthe present invention will be described with reference to FIG. 7. FIG. 7is a cross-sectional view of the semiconductor device according to thesecond embodiment. The semiconductor device according to the secondembodiment includes a MIS transistor, and a gate insulating film of theMIS transistor has the same structure as the gate insulating film of thesemiconductor device according to the first embodiment. As shown in FIG.7, a silicon oxide film 22 is provided on a p-type silicon substrate 21for element isolation. In the surface of the silicon substrate 21,shallow diffusion layers 30 a and deep diffusion layers 30 b areprovided as n-type source and drain by arsenic ion implantation. On thesurface of the silicon substrate 21, a gate insulating film 24 made ofHfSiSbOx is provided. Further, on the gate insulating film 24, a gateelectrode 26 made of polycrystalline silicon is provided. On the sidefaces of the gate electrode 26, a side wall 28 formed from, for example,a silicon oxide film is provided. On each of the deep diffusion layers30 b of the source/drain, a NiSi layer 32 is provided. The MIStransistor according to the second embodiment having such a structuredescribed above is covered with an interlayer insulating film 34.

Next, the manufacturing steps of the semiconductor device according tothe second embodiment will be described with reference to FIGS. 8A to10C. FIGS. 8A to 10C are cross-sectional views which show themanufacturing steps of the semiconductor device according to the secondembodiment.

First, an element isolation region 22 is formed on the semiconductorsubstrate 21. Here, as the semiconductor substrate 21, a p-type siliconsubstrate is used, and the element isolation region 22 is formed by awell-known method. Specifically, an STI (Shallow Trench Isolation)trench (having a depth of, for example, about 0.4 μm) is formed in thesubstrate 21, and then an silicon oxide film is deposited on the entiresurface of the substrate 21 by a CVD (Chemical Vapor Deposition) methodto fill the trench with the silicon oxide film. Thereafter, thesubstrate 21 is subjected to CMP (Chemo-Mechanical Polish) to obtain anelement isolation region 22 shown in FIG. 8A.

Next, boron (B) ions are implanted into an element region for thresholdvoltage adjustment. Thereafter, as shown in FIG. 8B, an insulating film24 of HfSiSbOx is formed by a sputtering method. In this case, threetargets, a hafnium target, a silicon target, and a antimony target to beadded as an impurity are used, and the ratio of Hf to the sum of Hf andSi (Hf/(Hf+Si)) in the insulating film 24 and the amount of Sb to becontained as an impurity in the insulating film 24 are controlled byadjusting the ratio of power applied to these targets. In the secondembodiment, the ratio, Hf/(Hf+Si) is set to 0.5, but can be set to anyvalue within the range of 0.3 to 1.0. Further, the amount of Sb is setto 1.0 atomic %. However, as described above with reference to the firstembodiment, the amount of Sb can be set to any value within the range of0.003 to 3 atomic %. It is to be noted that the amount of Sb added as animpurity was evaluated by XPS. The insulating film 24 may be anoxynitride film or a nitride film obtained by controlling the amounts ofnitrogen and oxygen to be mixed into an atmosphere for sputtering sothat the dielectric film can contain nitrogen. In the second embodiment,the temperature of the substrate at the time when the insulating film 24is formed is set to room temperature, but can be set to any value.Further, in the second embodiment, the thickness of the insulating film24 is set to 4 nm, but can be appropriately set to a value within therange of 2 to 5 nm.

Next, as shown in FIG. 8C, a polycrystalline silicon film for formingthe gate electrode 26 is deposited on the gate insulating film 24 by aCVD method in an atmosphere containing Si₂H₆ gas or SiH₄ gas.

Next, a resist pattern 40 is formed on the polycrystalline silicon film,and then the polycrystalline silicon film is patterned using the resistpattern 40 as a mask by reactive ion etching using CFx gas to therebyform the gate electrode 26 shown in FIG. 9A. Then, in a state where theresist pattern 40 remains on the gate electrode 26, the insulating film24 is etched using an aqueous hydrofluoric acid solution to form thegate insulting film 24 shown in FIG. 9B. As a result, the surface of thesubstrate 21 is exposed on both sides of the gate insulating film 24.

Thereafter, as shown in FIG. 9C, arsenic (As) ions are implanted intothe exposed substrate 21 to form shallow impurity regions 30 a. At thistime, ion implantation is carried out at an accelerating voltage of 200eV and a dosage of about 1×10¹⁵ cm⁻².

Next, the resist pattern 40 is removed. Thereafter, SiO₂ or SiN isdeposited on the entire surface by, for example, a CVD method, and thenoverall etching is carried out by anisotropic etching so that the gateside wall 28 having a thickness of 10 nm is formed on the side faces ofthe gate electrode 26 as shown in FIG. 10A.

Arsenic ions are implanted into the substrate 21 by the use of the gateside wall 28 and the gate electrode 26 as a mask under the conditionsof, for example, an accelerating voltage of 10 keV and a dosage of1×10¹⁵ cm⁻² to thereby form deep impurity regions 30 b as shown in FIG.10B. Then, heat treatment is carried out at a temperature of 600° C. orhigher for activation of the impurity to thereby form extension layers30 a and source/drain regions 30 b. Activation of the impurity ispreferably carried out at a high temperature of about 1,000° C. for ashort time of about 10 seconds.

Next, a Ni film is formed on the entire surface, and then heat treatmentis carried out at a temperature of about 400° C. to react exposedsilicon with Ni. Then, unreacted Ni is removed by etching using a mixedsolution of sulfuric acid and hydrogen peroxide. As a result, as shownin FIG. 10C, the Ni silicide (NiSi) layer 32 is formed on each of thesource/drain regions 30 b. At this time, although not shown in thedrawing, the Ni silicide layer is formed also on the upper surface ofthe gate electrode 26 made of polycrystalline silicon. Thereafter, asilicon oxide film is deposited on the entire surface by a CVD method toform the interlayer insulating film 34 shown in FIG. 7.

Although subsequent steps are not shown in drawings, according to awell-known method, it is possible to obtain a MOS structure with a firstlayer wiring. For example, contact holes are formed in the interlayerinsulating film 34 to expose the surface of the NiSi layer 32, and thenTiN as a barrier metal is deposited on the bottom surfaces of thecontact holes by CVD. Thereafter, W as a plug material is deposited onthe entire surface to fill the contact holes with W, and then the entiresurface is planarized by CMP. Then, an Al—Cu film as a wiring materialis deposited, and the Al—Cu film is patterned by photolithography tothereby obtain a MOS structure with a first layer wiring.

As in the case of the first embodiment, the second embodiment of thepresent invention can also provide a semiconductor device capable ofpreventing the deterioration of device characteristics as much aspossible and avoiding fluctuations in threshold voltage.

Further, as in the case of the first embodiment, it is possible to addthe same additive element to the N- and P-type MIS transistors, andtherefore a manufacturing process is simplified, thereby suppressing anincrease in manufacturing costs.

THIRD EMBODIMENT

Hereinbelow, a semiconductor device according to a third embodiment ofthe present invention will be described with reference to FIG. 11. FIG.11 is a cross-sectional view of the semiconductor device according tothe third embodiment. The semiconductor device according to the thirdembodiment has the same structure as the semiconductor device accordingto the second embodiment shown in FIG. 7 except that the gate electrode26 made of polysilicon is replaced with a gate electrode 27 made of ametal semiconductor compound, e.g., Ni silicide (NiSi).

Next, the manufacturing steps of the semiconductor device according tothe third embodiment will be described with reference to FIG. 12. FIG.12 is a cross-sectional view which shows the manufacturing step of thesemiconductor device according to the third embodiment.

The semiconductor device according to the third embodiment ismanufactured in the same manner as in the second embodiment until theinterlayer insulating film 34 is formed. Thereafter, as shown in FIG.12, a Ni film 29 is deposited on the entire surface, and is thensubjected to heat treatment at a temperature of about 400° C. so thatall the silicon atoms of the polycrystalline silicon film 26 react withNi to form Ni silicide. As described above, since heat treatment iscarried out at a low temperature of about 400° C., the profiles of theextension layers 30 a and source/drain regions 30 b are not changed.Into the polycrystalline silicon film 26, phosphorus (P), arsenic (As),antimony (Sb) or boron (B) may be previously introduced. After thecompletion of the reaction, unreacted Ni is removed using a mixedsolution of sulfuric acid and hydrogen peroxide to thereby form the gateelectrode 27 of NiSi shown in FIG. 11.

Although subsequent steps are not shown in drawings, according to awell-known method, it is possible to obtain a MOS structure with a firstlayer wiring. For example, contact holes are formed in the interlayerinsulating film 34 to expose the surface of the NiSi layer 32, and thenTiN as a barrier metal is deposited on the bottom surfaces of thecontact holes by CVD. Thereafter, W as a plug material is deposited onthe entire surface to fill the contact holes with W, and then the entiresurface is planarized by CMP. Then, an Al—Cu film as a wiring materialis deposited, and the Al—Cu film is patterned by photolithography tothereby obtain a MOS structure with a first layer wiring.

As in the case of the first embodiment, the third embodiment of thepresent invention can provide a semiconductor device capable ofpreventing the deterioration of device characteristics as much aspossible and avoiding fluctuations in threshold voltage.

Further, as in the case of the first embodiment, it is possible to addthe same additive element to the N- and P-type MIS transistors, andtherefore a manufacturing process is simplified, thereby suppressing anincrease in manufacturing costs.

FOURTH EMBODIMENT

Hereinbelow, a semiconductor device according to a fourth embodiment ofthe present invention will be described with reference to FIG. 13. Thesemiconductor device according to the fourth embodiment has the samestructure as the semiconductor device according to the second embodimentshown in FIG. 7 except that the insulting film 24 is replaced with agate insulating film 24 having a three-layer structure composed of aninsulating film 24 a of HfSiSbOx, an insulating film 24 b of HfSiOx, andan insulating film 24 c of HfSiSbOx.

Next, a manufacturing method of the semiconductor device according tothe fourth embodiment will be described with reference to FIGS. 14A to16C. FIGS. 14A to 16C are cross-sectional views which show themanufacturing steps of the semiconductor device according to the fourthembodiment.

First, an element isolation region 22 is formed on the semiconductorsubstrate 21. Here, as the semiconductor substrate 21, a p-type siliconsubstrate is used, and the element isolation region 22 is formed by awell-known method. Specifically, an STI trench (having a depth of, forexample, about 0.4 μm) is formed in the substrate 21, and then a siliconoxide film is deposited on the entire surface of the substrate 21 by aCVD method to fill the trench with the silicon oxide film. Thereafter,the substrate 21 is subjected to CMP to obtain an element isolationregion 22 shown in FIG. 14A.

Next, boron (B) ions are implanted into an element region for thresholdvoltage adjustment. Thereafter, as shown in FIG. 14B, the insulatingfilm 24 a of HfSiSbOx is formed by a sputtering method. In this case,three targets, a hafnium target, a silicon target, and a antimony targetto be added as an impurity are used, and the ratio of Hf to the sum ofHf and Si (Hf/(Hf+Si)) in the insulating film 24 a and the amount of Sbto be contained as an impurity in the insulating film 24 a arecontrolled by adjusting the ratio of power applied to these targets. Inthe fourth embodiment, the ratio, Hf/(Hf+Si) is set to 0.5, but can beset to any value within the range of 0.3 to 1.0. Further, the amount ofSb is set to 1.0 atomic %, but can be set to any value within the rangeof 0.003 to 3 atomic %. It is to be noted that the amount of Sb added asan impurity was evaluated by XPS. The insulating film 24 a may be anoxynitride film or a nitride film obtained by controlling the amounts ofnitrogen and oxygen to be mixed into an atmosphere for sputtering sothat the insulating film 24 a can contain nitrogen. In the fourthembodiment, the temperature of the substrate at the time when theinsulating film 24 a is formed is set to room temperature, but can beset to any value. Further, in the fourth embodiment, the thickness ofthe insulating film 24 a of HfSiSbOx is set to 1 nm, but can beappropriately set to a value within the range of 0.5 nm to 1.5 nm.

Next, the insulating film 24 b of HfSiOx is formed by sputtering in astate where no power is applied to the Sb target to stop sputtering fromthe Sb target. In the fourth embodiment, the thickness of the insulatingfilm 24 b made of HfSiOx is set to 2 nm, but can be appropriately set toa value within the range of 1 to 3 nm.

Then, the insulating film 24 c of HfSiSbOx is formed on the insulatingfilm 24 b by sputtering in the same manner as in the case of theinsulating film 24 a. In the fourth embodiment, the ratio, Hf/(Hf+Si) isset to 0.5, but can be set to any value within the range of 0.3 to 1.0.Further, the amount of Sb is set to 1.0 atomic %, but can be set to anyvalue within the range of 0.003 to 3 atomic %. As a matter of course,the amount of Sb contained in the insulting film 24 c of HfSiSbOx may bedifferent from the amount of Sb contained in the insulating film 24 a ofHfSiSbOx provided below the insulating film 24 c as long as it is withinthe range of 0.003 to 3 atomic %.

A method for depositing the gate insulating film 24 is not limited tothe method described above. For example, in a case where a CVD method isemployed, the insulating films 24 a and 24 c of HfSiSbOx may be formedby, for example, feeding a source gas of the additive element, e.g.,SbCl₃ gas only when the insulating films 24 a and 24 c are formed.

Next, as shown in FIG. 14C, a polycrystalline silicon film for formingthe semiconductor gate electrode 26 is deposited on the gate insulatingfilm 24 by a CVD method in an atmosphere containing Si₂H₆ or SiH₄.

Next, a resist pattern 40 is formed on the polycrystalline silicon film,and then the polycrystalline silicon film is patterned using the resistpattern 40 as a mask by reactive ion etching using CFx gas to therebyform the gate electrode 26 shown in FIG. 15A. Then, in a state where theresist pattern 40 remains on the gate electrode 26, the insulating film24 is etched using an aqueous hydrofluoric acid solution to form thegate insulting film 24 having a three-layer structure composed of theinsulating films 24 a, 24 b and 24 c as shown in FIG. 15B. As a result,the surface of the semiconductor substrate 21 is exposed on both sidesof the gate insulating film 24.

Next, as shown in FIG. 15C, arsenic ions are implanted into the exposedsubstrate 21 to form shallow impurity regions 30 a. At this time, ionimplantation is carried out at an accelerating voltage of 200 eV and adosage of about 1×10¹⁵ cm⁻² .

Next, the resist pattern 40 is removed. Thereafter, SiO₂ or SiN isdeposited on the entire surface by, for example, a CVD method, and thenoverall etching is carried out so that the gate side wall 28 having athickness of 10 nm is formed on the side faces of the gate electrode 26shown in FIG. 16A.

Arsenic ions are implanted into the substrate 21 by the use of the gateside wall 28 and the gate electrode 26 as a mask under the conditionsof, for example, an accelerating voltage of 10 keV and a dosage of1×10¹⁵ cm⁻² to thereby form deep impurity regions 30 b shown in FIG.16B. Then, heat treatment is carried out at a temperature of 600° C. orhigher for activation of the implanted impurity to thereby formextension layers 30 a and source/drain regions 30 b. Activation of theimpurity is preferably carried out at a high temperature of about 1,000°C. for a short time of about 10 seconds.

Next, a Ni film is formed on the entire surface, and is then subjectedto heat treatment at a temperature of about 400° C. After the completionof heat treatment, unreacted Ni is removed by etching using a mixedsolution of sulfuric acid and hydrogen peroxide. As a result, as shownin FIG. 16C, the Ni silicide (NiSi) layer 32 is formed on each of thesource/drain regions 30 b. At this time, although not shown in thedrawing, the Ni silicide layer is formed also on the upper surface ofthe gate electrode 26 made of polycrystalline silicon. Thereafter, asilicon oxide film is deposited on the entire surface by a CVD method toform the interlayer insulating film 34 shown in FIG. 13.

Although subsequent steps are not shown in drawings, according to awell-known method, it is possible to obtain a MOS structure with a firstlayer wiring. For example, contact holes are formed in the interlayerinsulating film 34 to expose the surface of the NiSi layer 32, and thenTiN as a barrier metal is deposited on the bottom surfaces of thecontact holes by CVD. Thereafter, W as a plug material is deposited onthe entire surface to fill the contact holes with W, and then the entiresurface is planarized by CMP. Then, an Al—Cu film as a wiring materialis deposited, and the Al—Cu film is patterned by photolithography tothereby obtain a MOS structure with a first layer wiring.

As in the case of the first embodiment, the fourth embodiment of thepresent invention can provide a semiconductor device capable ofpreventing the deterioration of device characteristics as much aspossible and avoiding fluctuations in threshold voltage.

Further, as in the case of the first embodiment, it is also possible toadd the same additive element to the N- and P-type MIS transistors, andtherefore a manufacturing process is simplified, thereby suppressing anincrease in manufacturing costs.

The gate insulating film 24 does not necessarily need to have athree-layer structure as shown in the fourth embodiment as long as theconcentration of the additive element is high in the vicinity of theinterface between the semiconductor substrate and the gate insulatingfilm or in the vicinity of the interface between the gate electrode andthe gate insulating film. For example, as shown in FIG. 17, the gateinsulating film 24 may be formed in such a manner that the concentrationof the additive element added to the gate insulating film 24 formed froma high-dielectric constant metal oxide film is increased from the middlepart of the gate insulating film 24 toward both of the interface betweenthe gate insulating film and the gate electrode and the interfacebetween the semiconductor substrate and the gate insulating film.Alternatively, the gate insulating film 24 may be formed in such amanner that the concentration of the additive element added to the gateinsulating film 24 is increased from the middle part of the gateinsulating film 24 toward at least one of the interface between the gateinsulating film and the gate electrode and the interface between thesemiconductor substrate and the gate insulating film. It is to be notedthat FIG. 17 shows a case where the concentration of the additiveelement is linearly increased from the middle part of the gateinsulating film toward the interface between the gate insulating filmand the gate electrode and the interface between the semiconductorsubstrate and the gate insulating film, but the gate insulating film 24may be alternatively formed in such a manner that the concentration ofthe additive element is increased stepwise. In this case, after the gateinsulating film 24 is formed in such a manner that the concentration ofthe additive element is increased stepwise, the gate insulating film 24may further be subjected to heat treatment at a temperature of about600° C. to diffuse the additive element toward the middle part of thegate insulating film 24.

As shown in the fourth embodiment, by forming the gate insulating filmin such a manner that the concentration of the additive element becomeshigh in the vicinity of the interface between the semiconductorsubstrate and the gate insulating film or in the vicinity of theinterface between the gate electrode and the gate insulating film, it ispossible to effectively compensate for oxygen vacancies likely to begenerated in the vicinity of the electrode or semiconductor substrateand to suppress an increase in gate leakage current or an increase infixed charge.

Various modifications can be made to the second, third, and fourthembodiments described above. For example, although antimony (Sb) is usedas the additive element in these embodiments, the additive element mayalternatively be another element of Group 15 such as phosphorus (P),arsenic (As) or bismuth (Bi), or an element of Group 16 such as sulfur(S), selenium (Se) or tellurium (Te), or an element of Group 5 such asvanadium (V), niobium (Nb) or tantalum (Ta), or an element of Group 6such as chromium (Cr), molybdenum (Mo) or tungsten (W). In a case whereany of Sb, P, As and Bi is used as the additive element, theconcentration of the additive element is preferably 0.1 atomic % or morebut 3 atomic % or less. By setting the concentration of such an additiveelement to a value within the above range, it is possible to effectivelycompensate for oxygen vacancies, generated in the step of forming thegate electrode or the step of heat treatment for activation, with theadditive element diffused in the gate insulating film. In a case whereany of S, Se, Te, V, Nb, Ta, Cr, Mo and W is used as the additiveelement, the concentration of the additive element is preferably 0.003atomic % or more but 3 atomic % or less. By setting the concentration ofsuch an additive element to a value within the above range, it ispossible to effectively compensate for oxygen vacancies generated in thestep of forming the gate electrode or the step of heat treatment foractivation. It is to be noted that the additive element is not limitedto one kind of element, and two or more kinds of additive elements maybe added simultaneously. In this case, as described above with referenceto the first embodiment, the total concentration of the additiveelements is preferably 3 atomic % or less.

Further, the silicide layer 32 formed on the source/drain regions 30 bmay be formed using CoSi₂ or TiSi₂ instead of NiSi.

Furthermore, SiGe may be used as the gate electrode. SiGe can be formedby, for example, mixing SiH₄ gas or Si₂H₆ gas with a gas containing Ge,such as Ge₂H₆ gas. Alternatively, silicide and/or germanide may be usedas the gate electrode. Examples of silicide include WSi₂, NiSi, CoSi₂,PtSi, and MoSi₂. Examples of germanide include WGe₂, NiGe, NiGe₂, CoGe₂,PtGe, and MoGe₂. A lanthanoide series metal silicide or germanide mayalso be used as the gate electrode.

Moreover, the gate insulating film 24 may be a film made of HfO₂, a filmmade of a mixture of HfO₂ and aluminum oxide, a film made of ZrO₂, afilm made of a mixture of ZrO₂ and silicon oxide, a film made of amixture of ZrO₂ and Al₂O₃, a film made of TiO₂, a film made of a mixtureof TiO₂ and silicon oxide, or a film made of a mixture of TiO₂ andAl₂O₃. Alternatively, the gate insulating film 24 may be made of alanthanoide series metal oxide typified by La₂O₃, a mixture of such alanthanoide series metal oxide and SiO₂, or a mixture of oxide of alanthanoide series metal such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb or Lu and Al₂O₃.

Moreover, the gate insulating film 24 may be formed by MOCVD, halide CVDor atomic layer deposition. Since an increase in leakage current iscaused by phase separation or crystallization which occurs in the filmdue to, for example, heat treatment for activation of the electrode, thegate insulating film is preferably nitrided. For example, the gateinsulating film can be nitrided by CVD in an atmosphere containing NH₃or N. For example, in the case of Hf, nitriding can be carried out byCVD using Hf(N(C₂H₅)₂)₄. The metal contained in the metal oxide can bechanged by selecting a precursor containing the metal and nitrogen.Alternatively, nitrogen activated by plasma may be added to anatmosphere or a formed film may be exposed to N plasma. In the case ofCVD, the additive element can be added by feeding a source gas of theadditive element such as SbCl₃ together with other gases. A method foradding the additive element is not limited to the method describedabove. For example, the additive element can be added by ionimplantation carried out after the gate insulating film is deposited.

It is to be noted that as shown in FIG. 18, an insulating film 25 madeof silicon oxide or silicon oxynitride may be provided between the gateinsulating film 24 and the gate electrode 26 to prevent oxygen (O) frompenetrating into the gate electrode. However, the thickness of theinsulating film 25 is preferably 2 nm or less to prevent an increase inleakage current caused by decrease in dielectric constant.

Further, as shown in FIG. 19, an insulating film 23 made of siliconoxide or silicon oxynitride may be provided between the gate insulatingfilm 24 and the semiconductor substrate 21 to prevent oxygen (O) frompenetrating into the semiconductor substrate. However, the thickness ofthe insulating film 23 is preferably 2 nm or less to prevent an increasein leakage current caused by decrease in dielectric constant.

In each of the second, third, and fourth embodiments, the MIS transistordirectly formed on the Si substrate has been described by way ofexample, but the present invention is not limited to such a structure.The present invention can also be applied to SOI (Silicon On Insulator)structures, vertical MIS transistors in which current flows in adirection perpendicular to a substrate, and vertical MIS transistors inwhich current flows in the side face of an Si pillar.

Further, also in a case where a substrate made of Ge, SiGe, strained Sior strained Ge is used instead of the silicon substrate, the sameeffects as described above can be obtained.

FIFTH EMBODIMENT

Hereinbelow, a semiconductor device according to a fifth embodiment ofthe present invention will be described with reference to FIGS. 20 to24B.

The semiconductor device according to the fifth embodiment is anonvolatile semiconductor memory device. FIG. 20 is a cross-sectionalview of the semiconductor device according to the fifth embodiment. Asilicon oxide film 52 is provided on a p-type silicon substrate 51 forelement isolation. In the silicon substrate 51, shallow diffusion layers58 a and deep diffusion layers 58 b are provided as n-type source anddrain by arsenic ion implantation. On the surface of the siliconsubstrate 51, a tunnel oxide film 53 made of oxynitride containingsilicon, oxygen and nitrogen as main components is provided. On thetunnel oxide film 53, a floating gate electrode 54 a made ofpolycrystalline silicon is provided. On the floating gate electrode 54a, an interelectrode insulating film 55 made of hafnium oxide (HfSiSbOx)is provided so as to have a thickness of 15 nm. On the interelectrodeinsulating film 55, a control gate electrode 54 b made ofpolycrystalline silicon is provided. The floating gate electrode 54 a,the interelectrode insulating film 55, and the control gate electrode 54b constitute a gate part 56. On the side and top surfaces of the gatepart 56 composed of the floating gate electrode 54 a, the interelectrodeinsulating film 55, and the control gate electrode 54 b, an insulatingfilm 57 made of silicon oxide is provided. The insulating film 57 andthe source and drain regions 58 b are covered with an interlayerinsulating film 59 made of silicon oxide. In the interlayer insulatingfilm 59, holes (not shown in the drawing) for making contact with thesource and drain regions 58 b and the control gate electrode 54 b areprovided, and these holes are filled with Al electrodes (not shown inthe drawing).

Next, a method for manufacturing the nonvolatile semiconductor memorydevice according to the fifth embodiment will be described withreference to FIGS. 21A to 24B.

First, as shown in FIG. 21A, the element isolation region 52 is formedon the semiconductor substrate 51. Here, a p-type Si substrate is usedas the semiconductor substrate 51, and the element isolation region 52is formed according to a well-known method. Specifically, an STI trench(having a depth of, for example, about 0.4 μm) is formed in thesubstrate 51, and then a silicon oxide film is deposited on the entiresurface of the substrate 51 by a CVD method to fill the trench with thesilicon oxide film. Thereafter, the substrate 51 is subjected to CMP toobtain an element isolation region 52 shown in FIG. 21A.

Next, as shown in FIG. 21B, a silicon oxide film is formed by, forexample, thermal oxidation using dry oxygen so as to have a thickness of7 nm, and then the silicon oxide film is exposed to, for example, anatmosphere of ammonia (NH₃) gas for introduction of a nitrogen atom, tothereby form the tunnel oxide film (i.e., a gate insulating film) 53made of oxynitride.

Then, as shown in FIG. 21C, the n-type polycrystalline silicon film 54 acontaining phosphorus is deposited on the tunnel oxide film 53 so as tohave a thickness of 200 nm.

Next, as shown in FIG. 22A, on the polycrystalline silicon film 54 a,the interelectrode insulating film 55 made of, for example, hafniumoxide containing antimony (Sb) as an impurity (HfSiSbOx) is formed by asputtering method so as to have a thickness of 15 nm. The interelectrodeinsulating film 55 made of HfSiSbOx is formed using three targets, an Hftarget, an Si target, and a target of Sb to be added as an impurity, andthe ratio of Hf to the sum of Hf and Si (Hf/(Hf+Si)) in theinterelectrode insulating film 55 of HfSiSbOx and the amount of Sb to becontained as an impurity in the HfSiSbOx film are controlled byadjusting the ratio of power applied to these targets. In the fifthembodiment, the ratio, Hf/(Hf+Si) is set to 0.5, but can be set to anyvalue within the range of 0.3 to 1.0. Further, the amount of Sb is setto 1.0 atomic %, but can be set to any value within the range of 0.003to 3 atomic %.

Then, as shown in FIG. 22B, heat treatment is carried out using dryoxygen at a temperature of 650° C. At this time, atomic oxygenintroduced into the interelectrode insulating film fills vacancies of,for example, oxygen and helps Sb atoms that have not been introducedinto the interelectrode insulating film formed by sputtering to beefficiently introduced into oxygen vacancy sites or hafnium vacancysites.

Next, as shown in FIG. 22C, the n-type polycrystalline silicon film 54 bcontaining phosphorus is deposited on the interelectrode insulating film55 so as to have a thickness of 200 nm.

Next, as shown in FIG. 23A, a resist pattern 60 is formed on the n-typepolycrystalline silicon film 54 b, and then the polycrystalline siliconfilm 54 b, the interelectrode insulating film 55, the polycrystallinesilicon film 54 a, and the tunnel oxide film 53 are patterned by areactive ion etching method using the resist pattern 60 as a mask tothereby form the gate part 56 and the gate insulating film 53. As aresult, the surface of the semiconductor substrate 51 is exposed on bothsides of the gate part 56.

Then, as shown in FIG. 23B, arsenic ions are implanted into an elementregion of the exposed substrate 51 at 200 eV at a dosage of about 1×10¹⁵cm⁻² to form shallow impurity regions 58 a. Thereafter, the resistpattern is removed.

Next, as shown in FIG. 24A, heat treatment is carried out in anoxidative atmosphere for the purpose of, for example, recovery fromdamage resulting from processing so that the oxide film 57 having athickness of about 3 nm is formed so as to cover the side and topsurfaces of the gate part 56.

Next, as shown in FIG. 24B, ions of, for example, phosphorus areimplanted into the entire surface at a dosage of 3×10¹⁵ cm⁻². Theimplanted phosphorus ions are distributed around a peak depth dependentupon the acceleration energy in the silicon substrate 51. Thereafter,phosphorus is diffused in the silicon substrate 51 and activated by, forexample, carrying out heat treatment at 1,000° C. for 20 seconds tothereby form the diffusion layers 58 b as source/drain regions. Then, asilicon oxide film having a thickness of 300 nm is deposited on theentire surface by a CVD method to form the interlayer insulating film 59shown in FIG. 20.

Although subsequent steps are not shown in drawings, according to awell-known method, it is possible to obtain a MOS structure with a firstlayer wiring. For example, contact holes are formed in the interlayerinsulating film 59 to expose the surface of the source/drain regions 58b, and then TiN as a barrier metal is deposited on the bottom surfacesof the contact holes by CVD. Thereafter, W as a plug material isdeposited on the entire surface to fill the contact holes with W, andthen the entire surface is planarized by CMP. Then, an Al-Cu film as awiring material is deposited, and the Al-Cu film is patterned byphotolithography to thereby obtain a MOS structure with a first layerwiring.

According to the fifth embodiment, since the interelectrode insulatingfilm 55 provided between the floating gate electrode 54 a and thecontrol gate electrode 54 b is made of hafnium oxide containing antimonyat 1 atomic %, it is possible to compensate for vacancies of, forexample, oxygen, thereby making it possible to provide a nonvolatilesemiconductor memory device with a low leakage current.

As has been described above, according to the fifth embodiment, it ispossible to prevent the deterioration of device characteristics as muchas possible.

Various modifications can be made to the fifth embodiment describedabove. For example, although antimony (Sb) is used as the additiveelement in the fifth embodiment, the additive element may alternativelybe another element of Group 15 such as phosphorus, arsenic or bismuth,or an element of Group 16 such as sulfur, selenium or tellurium, or anelement of Group 5 such as vanadium, niobium or tantalum, or an elementof Group 6 such as chromium, molybdenum or tungsten. In a case where anyof Sb, P, As and Bi is used as the additive element, the concentrationof the additive element is preferably 0.1 atomic % or more but 3 atomic% or less. By setting the concentration of such an additive element to avalue within the above range, it is possible to effectively compensatefor oxygen vacancies, generated in the step of forming the gateelectrode or the step of heat treatment for activation, with theadditive element diffused in the interelectrode insulating film. In acase where any of S, Se, Te, V, Nb, Ta, Cr, Mo and W is used as theadditive element, the concentration of such an additive element ispreferably 0.003 atomic % or more but 3 atomic % or less. By setting theconcentration of such an additive element to a value within the aboverange, it is possible to effectively compensate for oxygen vacanciesgenerated in the step of forming the gate electrode or the step of heattreatment for activation. It is to be noted that the additive element isnot limited to one kind of element, and two or more kinds of additiveelements may be added simultaneously. In this case, as described abovewith reference to the first embodiment, the total concentration of theadditive elements is preferably 3 atomic % or less.

Further, SiGe may be used as the floating gate electrode 54 a and thecontrol gate electrode 54 b. SiGe can be formed by, for example, mixingSiH₄ gas or Si₂H₆ gas with a gas containing Ge such as Ge₂H₆ gas.Alternatively, silicide and/or germanide may be used as the floatinggate electrode 54 a and the control gate electrode 54 b. Examples ofsilicide include WSi₂, NiSi, CoSi₂, PtSi, and MoSi₂. Examples ofgermanide include WGe₂, NiGe, NiGe₂, CoGe₂, PtGe, and MoGe₂. Alanthanoide series metal silicide or germanide may also be used as thefloating gate electrode 54 a and the control gate electrode 54 b.

Furthermore, the interelectrode insulating film 55 may be a film made ofHfO₂, a film made of a mixture of HfO₂ and aluminum oxide, a film madeof ZrO₂, a film made of a mixture of ZrO₂ and silicon oxide, a film madeof a mixture of ZrO₂ and Al₂O₃, a film made of TiO₂, a film made of amixture of TiO₂ and silicon oxide, or a film made of a mixture of TiO₂and Al₂O₃. Alternatively, the interelectrode insulating film 55 may bemade of a lanthanoide series metal oxide typified by La₂O₃, a mixture ofsuch a lanthanoide series metal oxide and SiO₂, an oxide of alanthanoide series metal such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb or Lu, or a mixture of such a lanthanoide series metaloxide and Al₂O₃.

Moreover, the interelectrode insulating film 55 may be formed by MOCVD,halide CVD or atomic layer deposition. Since an increase in leakagecurrent is caused by phase separation or crystallization which occurs inthe film due to, for example, heat treatment for activation of theelectrode, the insulating film 55 is preferably nitrided. For example,the insulating film can be nitrided by CVD in an atmosphere containingNH₃ or N. For example, in the case of Hf, nitriding can be carried outby CVD using Hf(N(C₂H₅)₂)₄. The metal contained in the metal oxide canbe changed by selecting a precursor containing the metal and nitrogen.Alternatively, nitrogen activated by plasma may be contained in anatmosphere or a formed film may be exposed to N plasma. In the case ofCVD, the additive element can be added by feeding a source gas of theadditive element such as SbCl₃ together with other gases. A method foradding the additive element is not limited to the method describedabove. For example, the additive element can be added by ionimplantation carried out after the interelectrode insulating film isdeposited.

As in the case of the semiconductor device described with reference toFIG. 18, an Si oxide film or an Si oxynitride film may be providedbetween the interelectrode insulating film 55 and the floating gateelectrode 54 a or between the interelectrode insulating film 55 and thecontrol gate electrode 54 b. However, the thickness of the Si oxide filmor the Si oxynitride film is preferably 2 nm or less to prevent anincrease in leakage current caused by decrease in dielectric constant.

Further, Ge, SiGe, strained Si or strained Ge can be used as thesemiconductor substrate 51. Also in this case, it is possible tomanufacture a nonvolatile semiconductor memory device having the sameeffects as obtained by the fifth embodiment.

As has been described above, according to each of the embodiments of thepresent invention, it is possible to prevent the deterioration of devicecharacteristic as much as possible.

Additional advantages and modifications will readily occur to thoseskilled in the art. Therefore, the invention in its broader aspects isnot limited to the specific details and representative embodiments shownand described herein. Accordingly, various modifications may be madewithout departing from the spirit or scope of the general inventiveconcepts as defined by the appended claims and their equivalents.

1-20. (canceled)
 21. A semiconductor device comprising: a semiconductorsubstrate; a gate insulating film provided above the semiconductorsubstrate and containing a metal, oxygen and an additive element; a gateelectrode provided above the gate insulating film; and source/drainregions provided in the semiconductor substrate on both sides of thegate electrode, the additive element being at least one element selectedfrom elements of Group 5 except tantalum, Group 6, Group 15 exceptnitrogen, phosphorus, and antimony, and Group 16 at a concentration of0.003 atomic % or more but 3 atomic % or less.
 22. The semiconductordevice according to claim 21, wherein the additive element is at leastone element selected from the group consisting of arsenic, and bismuthat a concentration of 0.1 atomic % or more but 3 atomic % or less. 23.The semiconductor device according to claim 21, wherein the additiveelement is at least one element selected from the group consisting ofsulfur, selenium, tellurium, vanadium, niobium, chromium, molybdenum andtungsten at a concentration of 0.003 atomic % or more but 3 atomic % orless.
 24. The semiconductor device according to claim 21, wherein thegate insulating film contains bonding between the metal and the additiveelement.
 25. The semiconductor device according to claim 21, wherein thegate insulating film contains bonding between the oxygen and theadditive element.
 26. The semiconductor device according to claim 21,further comprising an insulating film made of Si oxide or Si oxynitrideand provided either between the gate insulating film and the gateelectrode or between the gate insulating film and the semiconductorsubstrate.
 27. The semiconductor device according to claim 21, whereinthe metal is at least one element selected from the group consisting ofHf, Zr, Ti, and lanthanoide series elements.